Answers to Exercise 3.

2
Molecular Orbital Energy Level Diagrams: Heteronuclear Diatomics

1.
(a) The electron configuration for 𝐿𝐿𝐿𝐿 is 1𝑠𝑠 2 2𝑠𝑠1 , so 𝐿𝐿𝐿𝐿 has 1 valence electron.
The electron configuration for 𝐻𝐻 is 1𝑠𝑠1 , so 𝐻𝐻 has 1 valence electron.
Therefore, 𝐿𝐿𝐿𝐿𝐿𝐿 has 2 valence electrons.
∗
2σ
LUMO

2s

1s

HOMO 1σ

Li LiH H
If your pictures look the same as the ones on the diagram for 𝐻𝐻𝐻𝐻𝐻𝐻 + , that’s fine.
The computer shows that the polarization is even stronger in 𝐿𝐿𝐿𝐿𝐿𝐿 than in 𝐻𝐻𝐻𝐻𝐻𝐻 + .

(b) Li H

The Lewis diagram gives a bond order of 1 since the Lewis diagram shows a single bond.
2−0 2
The bond order calculated from the molecular orbital energy level diagram is 2
= 2 = 1.
They match!

(c) H is more electronegative than Li, so the 𝐿𝐿𝐿𝐿 − 𝐻𝐻 bond is polar (with H as the negative end).
The electrons in 𝐿𝐿𝐿𝐿𝐿𝐿 are in the 1𝜎𝜎 orbital which is strongly polarized toward H. As such,
the electrons in 𝐿𝐿𝐿𝐿𝐿𝐿 spend more time near H than near Li. This means that H should be
the negative end of the 𝐿𝐿𝐿𝐿 − 𝐻𝐻 bond, supporting the prediction based on electronegativities.

(d) If 𝐿𝐿𝐿𝐿𝐿𝐿 reacted as an electron pair acceptor in a reaction, the LUMO (2𝜎𝜎 ∗ ) would accept the
electron pair. This orbital is strongly polarized toward Li, so Li would be the atom
accepting the electrons:

donor + Li H donor Li + H

Adding electrons to the antibonding 2𝜎𝜎 ∗ orbital would reduce the 𝐿𝐿𝐿𝐿 − 𝐻𝐻 bond order from
1 to 0, resulting in breaking of the 𝐿𝐿𝐿𝐿 − 𝐻𝐻 bond.
2.
(a) The electron configuration for 𝑂𝑂 is 1𝑠𝑠 2 2𝑠𝑠 2 2𝑝𝑝4 , so 𝑂𝑂 has 6 valence electrons.
The electron configuration for 𝐻𝐻 is 1𝑠𝑠1 , so 𝐻𝐻 has 1 valence electron.
Therefore, 𝑂𝑂𝑂𝑂 would have 7 valence electrons, and 𝑂𝑂𝑂𝑂 − has 8 valence electrons.
Grouping the valence AOs by symmetry and energy gives:
• one pi-symmetric 2𝑝𝑝𝑥𝑥 orbital on 𝑂𝑂,
• one pi-symmetric 2𝑝𝑝𝑦𝑦 orbital on 𝑂𝑂,
• one sigma-symmetric 2𝑠𝑠 orbital on 𝑂𝑂 that is more than 1 Ry away from the nearest
other sigma-symmetric orbital, and
• two sigma-symmetric AOs close enough in energy to combine: 1𝑠𝑠(𝐻𝐻) and 2𝑝𝑝𝑧𝑧 (𝑂𝑂).

∗
LUMO 3σ

1s
2p 1πnb
HOMO
E
2σ

2s 1σnb

-
O OH H

If your picture of 1𝜎𝜎𝑛𝑛𝑛𝑛 just looks like a 2𝑠𝑠 orbital on 𝑂𝑂, that’s fine.

(b)
O H

The Lewis diagram gives a bond order of 1 since the Lewis diagram shows a single bond.
2−0 2
The bond order calculated from the molecular orbital energy level diagram is 2
= 2 = 1.
They match!

(c) The HOMO and LUMO have been labeled on the diagram in part (a).
Since 𝑂𝑂𝑂𝑂 − is an anion, it is more likely to react as an electron pair donor.
As an electron pair donor, 𝑂𝑂𝑂𝑂 − will react with its HOMO.
The HOMO (1𝜋𝜋𝑛𝑛𝑛𝑛 ) is polarized toward O, so 𝑂𝑂𝑂𝑂 − will tend to donate an electron pair
from the oxygen atom. Since the HOMO is nonbonding, donating a pair of electrons from
it will not change the 𝑂𝑂 − 𝐻𝐻 bond order.

acceptor + O H acceptor O H
3.
(a) The electron configuration for 𝑁𝑁 is 1𝑠𝑠 2 2𝑠𝑠 2 2𝑝𝑝3 , so 𝑁𝑁 has 5 valence electrons.
The electron configuration for 𝑂𝑂 is 1𝑠𝑠 2 2𝑠𝑠 2 2𝑝𝑝4 , so 𝑂𝑂 has 6 valence electrons.
Therefore, 𝑁𝑁𝑁𝑁 would have 11 valence electrons, and 𝑁𝑁𝑁𝑁+ has 10 valence electrons.
Grouping the valence AOs by symmetry and energy gives:
• two pi-symmetric 2𝑝𝑝𝑥𝑥 orbitals, one from each atom,
• two pi-symmetric 2𝑝𝑝𝑦𝑦 orbitals, one from each atom,
• four sigma-symmetric orbitals close enough in energy to combine: 2𝑠𝑠(𝑁𝑁), 2𝑠𝑠(𝑂𝑂),
2𝑝𝑝𝑧𝑧 (𝑁𝑁) and 2𝑝𝑝𝑧𝑧 (𝑂𝑂).

∗
4σ

∗
LUMO 2π

2p

2p
HOMO 3σ

E 1π

∗
2σ

2s

2s
1σ

+
N NO O

1𝜎𝜎 and 1𝜋𝜋 are slightly polarized toward O. 4𝜎𝜎 ∗ and 2𝜋𝜋 ∗ are slightly polarized toward N. Because
the difference in energy between the AOs of N and the AOs of O is not very large, this polarization
is not very easy to see (except in 2𝜋𝜋 ∗ ). It is even harder to predict and see the polarization in 2𝜎𝜎 ∗
and 3𝜎𝜎 (since they are made from both 2𝑠𝑠 and 2𝑝𝑝𝑧𝑧 orbitals from both N and O).

(b) The HOMO and LUMO have been labeled on the diagram in part (a).
Since 𝑁𝑁𝑁𝑁+ is a cation, it is more likely to react as an electron pair acceptor.
As an electron pair acceptor, 𝑁𝑁𝑁𝑁+ will react with its LUMO.
The LUMO (2𝜋𝜋 ∗ ) is polarized toward N, so 𝑁𝑁𝑁𝑁+ will tend to accept an electron pair at the
nitrogen atom. Since the LUMO is antibonding, adding a pair of electrons to it will reduce
the bond order from 3 to 2.

donor N
donor + N O
O